KR101336540B1 - Alumina particles wrapped in graphene sheets, the manufacturing method thereof, alumina particles thereby, graphene-TiO2 paste, the manufacturing method of the graphene-TiO2 paste, the method for manufacturing dye-sensitized solar cell, and the dye-sensitized solar cell thereby - Google Patents
Alumina particles wrapped in graphene sheets, the manufacturing method thereof, alumina particles thereby, graphene-TiO2 paste, the manufacturing method of the graphene-TiO2 paste, the method for manufacturing dye-sensitized solar cell, and the dye-sensitized solar cell thereby Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims 14
- 238000000034 method Methods 0.000 title description 8
- 239000002245 particle Substances 0.000 title description 3
- 239000000843 powder Substances 0.000 claims abstract description 84
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 42
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011858 nanopowder Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000012495 reaction gas Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000003028 elevating effect Effects 0.000 claims 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 14
- 238000000619 electron energy-loss spectrum Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 5
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- 229910002804 graphite Inorganic materials 0.000 description 4
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- 238000001069 Raman spectroscopy Methods 0.000 description 3
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- 239000002131 composite material Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- SWWLEHMBKPSRSI-UHFFFAOYSA-N 1-hexyl-2,3-dimethylimidazol-3-ium Chemical compound CCCCCCN1C=C[N+](C)=C1C SWWLEHMBKPSRSI-UHFFFAOYSA-N 0.000 description 1
- YYXZQUOJBJOARI-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;iodide Chemical compound [I-].CCCCCCN1C=C[N+](C)=C1C YYXZQUOJBJOARI-UHFFFAOYSA-M 0.000 description 1
- LTNAYKNIZNSHQA-UHFFFAOYSA-L 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium(2+);dithiocyanate Chemical compound N#CS[Ru]SC#N.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 LTNAYKNIZNSHQA-UHFFFAOYSA-L 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
본 발명은, AlN 분말들을 준비하는 단계와, 상기 AlN 분말들을 부분 또는 전체로서 일산화탄소 가스를 포함하는 반응가스 분위기에서 하소(calcining)하여 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계를 포함하는 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 방법을 제공한다.
상기로부터, 그래핀 시트들로 싸인 알루미나 분말들을 용이하게 제조할 수 있다. 상기 알루미나 분말들과 TiO2 나노분말들의 혼합 분말들을 이용하여 제조된 그래핀-TiO2 페이스트로 염료 감응형 태양전지의 TiO2층을 형성하면, 상기 그래핀 시트들에 싸인 알루미나 분말들이 TiO2 나노분말들과 혼합되어 효과적인 전자 이동 매체로서 작용한다. 따라서, TiO2로부터 전극층으로의 전자 이동이 증가하고, 재결합률이 감소한다. 이로부터, 염료 감응형 태양전지의 에너지 변환 효율이 크게 향상된다.The present invention includes preparing AlN powders, and calcining the AlN powders in a reaction gas atmosphere containing carbon monoxide gas as a part or the whole to produce alumina powders wrapped with graphene sheets. Provided is a method of making alumina powders wrapped with pin sheets.
From the above, alumina powders wrapped with graphene sheets can be easily produced. When forming the TiO 2 layer of the alumina powder and TiO 2 nano powder yes DSSC to pin 2 -TiO paste prepared using the powder mixture of the alumina powder to yes wrapped fin sheets are TiO 2 nano It is mixed with the powders to act as an effective electron transfer medium. Therefore, electron transfer from TiO 2 to the electrode layer increases, and the recombination rate decreases. From this, the energy conversion efficiency of the dye-sensitized solar cell is greatly improved.
Description
본 발명은 그래핀 시트들로 싸인 알루미나 분말들, 알루미나 분말의 제조방법, 이의 제조방법에 의하여 제조된 알루미나 분말들, 그래핀-TiO2 페이스트, 그래핀-TiO2 페이스트 제조 방법, 염료 감응형 태양전지의 제조방법, 및 이의 제조방법에 의하여 제조된 염료 감응형 태양 전지에 관한 것이다.The present invention provides alumina powders wrapped with graphene sheets, a method for producing alumina powder, alumina powders prepared by the method, a graphene-TiO 2 paste, a graphene-TiO 2 paste, a dye-sensitized aspect It relates to a method for producing a battery, and a dye-sensitized solar cell manufactured by the method for producing the battery.
단일층의 2차원 탄소 격자 구조를 가지는 그래핀은 최근에 전기적, 열적 및 기계적인 특성에 의하여 상당한 관심을 가지고 연구되고 있다. 그래핀 시트를 제조하는 방법은 아직 다양하게 연구되고 있다.Graphene having a single layered two-dimensional carbon lattice structure has recently been studied with considerable interest due to its electrical, thermal and mechanical properties. The method for producing the graphene sheet has yet to be variously studied.
그래핀 시트를 제조하는 주요한 방법에는 벌크 흑연의 미세 기계적인 떼어냄(micromechanical cleavage), 산화-박리-환원(oxidation-exfoliation-reduction), 실리콘 카바이드의 고 진공 그래파이트화(ultrahigh vacuum graphization of silicon carbide), 카본 소스로서 메탄을 이용하는 플라즈마 이용 화학 기상 증착 및 마이크로웨이브 플라즈마 반응기를 이용한 기상 합성 등이 있다. The main methods for producing graphene sheets include micromechanical cleavage of bulk graphite, oxidation-exfoliation-reduction, and ultrahigh vacuum graphization of silicon carbide. And chemical vapor deposition using plasma using methane as a carbon source and gas phase synthesis using a microwave plasma reactor.
본 발명은 그래핀 시트들로 싸인 알루미나 분말들, 알루미나 분말의 제조방법, 이의 제조방법에 의하여 제조된 알루미나 분말들, 그래핀-TiO2 페이스트, 그래핀-TiO2 페이스트 제조 방법, 염료 감응형 태양전지의 제조방법, 및 이의 제조방법에 의하여 제조된 염료 감응형 태양 전지를 제공하는데 목적이 있다.The present invention provides alumina powders wrapped with graphene sheets, a method for producing alumina powder, alumina powders prepared by the method, a graphene-TiO 2 paste, a graphene-TiO 2 paste, a dye-sensitized aspect It is an object of the present invention to provide a method for producing a battery, and a dye-sensitized solar cell manufactured by the method.
본 발명은, 그래핀 시트들로 싸인 알루미나 분말들을 제공한다.The present invention provides alumina powders wrapped with graphene sheets.
본 발명의 다른 측면에 따르면, (a) AlN 분말들을 준비하는 단계와, (b) 상기 AlN 분말들을 부분 또는 전체로서 일산화탄소 가스를 포함하는 반응가스 분위기에서 하소(calcining)하여 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계를 포함하는 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 방법을 제공한다.According to another aspect of the present invention, (a) preparing the AlN powders, (b) calcining the AlN powders in a reaction gas atmosphere containing carbon monoxide gas as part or all, wrapped with graphene sheets It provides a method for producing alumina powders wrapped with graphene sheets comprising the step of producing alumina powders.
본 발명에 있어서, 상기 (b) 단계에서, 상기 반응 가스는 아르곤 가스를 더 포함할 수 있으며, 이 때 상기 반응 가스가 설정 속도로 흐르고 있는 상태에서, 상기 AlN 분말들을 점차 가열하여 온도를 상승시킬 수 있다.In the present invention, in the step (b), the reaction gas may further include an argon gas, at which time the AlN powders are gradually heated to raise the temperature while the reaction gas is flowing at a set speed. Can be.
본 발명의 또 다른 측면에 따르면, 본 발명은, 상기 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 방법에 의하여 제조되는 그래핀 시트들로 싸인 알루미나 분말들을 제공한다.According to another aspect of the present invention, the present invention provides alumina powders wrapped with graphene sheets produced by the method for producing alumina powders wrapped with the graphene sheets.
본 발명의 또 다른 측면에 따르면, 본 발명은, 그래핀 시트들로 싸인 알루미나 분말들과 TiO2 나노분말들의 혼합 분말을 포함하는 그래핀-TiO2 페이스트를 제공한다.According to another aspect of the present invention, the present invention provides a graphene-TiO 2 paste comprising a mixed powder of alumina powders and TiO 2 nanopowders wrapped with graphene sheets.
본 발명의 또 다른 측면에 따르면, 본 발명은, AlN 분말들을 준비하는 단계와, 상기 AlN 분말들을 부분 또는 전체로서 일산화탄소 가스를 포함하는 반응가스 분위기에서 하소(calcining)하여 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계와, 상기 알루미나 분말들과 TiO2 나노분말들의 혼합 분말을 이용하여 그래핀-TiO2 페이스트를 제조하는 단계를 포함하는 그래핀-TiO2 페이스트 제조 방법을 제공한다.According to another aspect of the present invention, the present invention provides alumina wrapped with graphene sheets by preparing AlN powders and calcining the AlN powders in a reaction gas atmosphere containing carbon monoxide gas as part or all. It provides a graphene-TiO 2 paste manufacturing method comprising the steps of preparing powders, and preparing a graphene-TiO 2 paste using a mixture of the alumina powders and TiO 2 nanopowders.
본 발명의 또 다른 측면에 따르면, 본 발명은, AlN 분말들을 준비하는 단계와, 상기 AlN 분말들을 부분 또는 전체로서 일산화탄소 가스를 포함하는 반응가스 분위기에서 하소(calcining)하여 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계와, 상기 알루미나 분말들과 TiO2 나노분말들의 혼합 분말을 이용하여 그래핀-TiO2 페이스트를 제조하는 단계와, 기판 상에 전극층을 형성하는 단계와, 상기 전극층 상에 상기 그래핀-TiO2 페이스트를 도포하여 TiO2층을 형성하는 단계를 포함하는 염료 감응형 태양전지의 제조방법 및 이에 의하여 제조된 염료 감응형 태양전지를 제공한다.According to another aspect of the present invention, the present invention provides alumina wrapped with graphene sheets by preparing AlN powders and calcining the AlN powders in a reaction gas atmosphere containing carbon monoxide gas as part or all. preparing a powder and forming a step, and a electrode layer on a substrate by using a powder mixture of the alumina powder and TiO 2 nano powder prepared So the pin -TiO 2 and the paste, well onto the electrode layer It provides a method for producing a dye-sensitized solar cell comprising applying a pin-TiO 2 paste to form a TiO 2 layer and a dye-sensitized solar cell produced thereby.
본 발명에 따르면, 그래핀 시트들로 싸인 알루미나 분말들을 용이하게 제조할 수 있다. 상기 알루미나 분말들과 TiO2 나노분말들의 혼합 분말들을 이용하여 제조된 그래핀-TiO2 페이스트로 염료 감응형 태양전지의 TiO2층을 형성하면, 그래핀 시트들에 싸인 알루미나 분말들이 TiO2 나노분말들과 혼합되어 효과적인 전자 이동 매체로서 작용한다. 따라서, TiO2로부터 전극층으로의 전자 이동이 증가하고, 재결합률이 감소한다. 이로부터, 염료 감응형 태양전지의 에너지 변환 효율이 크게 향상된다.According to the present invention, alumina powders wrapped with graphene sheets can be easily produced. When forming the TiO 2 layer of the alumina powder and TiO 2 nano powder yes DSSC to pin 2 -TiO paste prepared using the powder mixture of yes to sign the alumina powder to the pin seat TiO 2 nano powder Mixed with them to act as an effective electron transfer medium. Therefore, electron transfer from TiO 2 to the electrode layer increases, and the recombination rate decreases. From this, the energy conversion efficiency of the dye-sensitized solar cell is greatly improved.
도 1은 본 발명의 일 실시예에 따라 제조된 샘플A 및 샘플B와 AlN 분말의 XRD 패턴을 보여준다.
도 2는 도 1의 샘플 A 및 샘플 B의 라만 스펙트럼을 보여준다.
도 3a는 도 1의 샘플 B를 고 분해능 투과 전자 현미경(HRTEM)으로 촬영한 사진이다.
도 3b는 도 3a의 ⓐ위치 및 ⓑ위치에서의 EELS 스펙트럼이다.
도 4는 그래핀 시트들에 싸인 알루미나 분말들을 가지는 염료 감응형 태양전지 및 이를 가지지 않는 염료 감응형 태양전지에서의 광전류-전압 곡선이다.Figure 1 shows the XRD pattern of Sample A and Sample B and AlN powder prepared according to an embodiment of the present invention.
FIG. 2 shows Raman spectra of Samples A and B of FIG. 1.
FIG. 3A is a photograph taken of high resolution transmission electron microscope (HRTEM) of sample B of FIG. 1.
3B is an EELS spectrum at positions ⓐ and ⓑ of FIG. 3A.
4 is a photocurrent-voltage curve in a dye-sensitized solar cell with alumina powders wrapped in graphene sheets and a dye-sensitized solar cell without it.
최근 들어, 본 출원인은 황화알루미늄(Al2S3)에 의한 일산화탄소의 환원에 의하여 그래핀 시트를 제조하였다. 본 실시예에서는, 일산화탄소 가스에 의하여 그래핀 시트를 합성하는 방법이 제시되며, 일산화탄소는 질화알루미늄 (AlN) 분말에 의하여 환원된다. 질화알루미늄과 일산화탄소의 반응은 알루미나(Al2O3)의 열탄소환원질화 반응(carbothermal reduction and nitridation, 이하 "CRN" 이라고 함)의 역반응이다. CRN 반응의 반응식은 다음과 같다.
Recently, the applicant has produced a graphene sheet by reduction of carbon monoxide by aluminum sulfide (Al 2 S 3 ). In this embodiment, a method for synthesizing the graphene sheet by carbon monoxide gas is presented, and carbon monoxide is reduced by aluminum nitride (AlN) powder. The reaction of aluminum nitride with carbon monoxide is a reverse reaction of the carbonaceous reduction and nitridation of alumina (Al 2 O 3 ) (hereinafter referred to as "CRN"). The scheme of the CRN reaction is as follows.
Al2O3 (s) + 3C (s) + N2 (g) → 2AlN (s) + 3 CO (g) (이하, "반응식1"이라 함)
Al 2 O 3 (s) + 3C (s) + N 2 (g) → 2AlN (s) + 3 CO (g) (hereinafter referred to as "
CRN 방법은 AlN 분말을 합성하는 가장 유용한 방법의 하나이다. 본 발명의 그래핀 시트는, 분말 X선 회절 (XRD), 라만 분광법, 전자 에너지 손실 분광법(electron energy loss spectroscopy), 고 분해능 투과 전자 현미경 (HRTEM)에 의하여 특성 평가되었다. 여기에서, 알루미나 분말을 싸고 있는 몇 층의 그래핀 시트가 확인되었는데, 이러한 알루미나 분말은 메소포러스(mesoporous) TiO2 층들에 기반을 둔 염료 감응형 태양 전지에 적용될 수 있다.The CRN method is one of the most useful methods for synthesizing AlN powders. Graphene sheets of the present invention were characterized by powder X-ray diffraction (XRD), Raman spectroscopy, electron energy loss spectroscopy, and high resolution transmission electron microscopy (HRTEM). Here, several layers of graphene sheets surrounding the alumina powder have been identified, which can be applied to dye-sensitized solar cells based on mesoporous TiO 2 layers.
염료 감응형 태양 전지(이하, "DSSC" 또는 "DSSCs"라 함)는 실리콘 기반의 태양 전지의 저비용 대안으로 연구되고 있지만, 30㎚ 보다 작은 나노분말로 이루어진 메소포러스 TiO2 층은 TiO2와 전해액 사이의 경계면에서 공핍층을 만들지 않아서, 역전자이동이 크게 일어난다. 그래핀은 무질량 상대론적 분말(massless relativistic particles)과 제로(zero) 밴드 갭을 가져서, 전기 전도도가 우수하기 때문에, 메소포러스 TiO2 전극들에 있는 그래핀은 전하 분리에 이롭고 재결합율을 낮춘다고 알려져 있다.
Dye-sensitized solar cells (hereinafter referred to as "DSSCs" or "DSSCs") are being studied as low-cost alternatives to silicon-based solar cells, but a mesoporous TiO 2 layer consisting of nanopowders smaller than 30 nm may contain TiO 2 and electrolytes. Since no depletion layer is created at the interface between them, reverse electron transfer occurs largely. Because graphene has massless relativistic particles and zero band gaps, and because of its good electrical conductivity, graphene on mesoporous TiO 2 electrodes is beneficial for charge separation and lowers recombination rates. Known.
1. 그래핀 시트들로 싸인 알루미나 분말들의 제조1. Preparation of Alumina Powders Wrapped with Graphene Sheets
AlN 분말은 질소 기체 분위기에 1300℃로, 5시간 동안 (하이드록소)(수시네이토) Al(Ⅲ) ((hydroxo)(succinato)Al(III)) 착물을 하소(calcining)하여 제조한다. 알루미나 도가니에 상기 분말을 담은 다음, 36㎜의 내경을 가지는 알루미나 튜브 내에 넣고, 200㎖/min 으로 흐르는 아르곤 및 10 vol% 일산화탄소의 혼합 가스(이하에서 "10 vol% CO/Ar"이라고 함) 내에서 5℃/min의 속도로 1400℃까지 가열된다. 이러한 합성 생성물은 분말 XRD(PANalytical X'Pert PRO MPD X-ray diffractometer with Cu-Ka radiation operating at 40 kV and 30 mA)에 의하여 분석되었다. 상기 합성 생성물 내의 카본 함유량은 CHN 원소 분석기 (CHN elemental analyzer, Flash 1112, Thermo Fischer Scientific)에 의하여 결정된다. 라만 스펙트럼(Raman spectrum)는 마이크로 라만 시스템에 의하여 측정되었다. He-Ne 레이저(632.8 nm, 3mW) 의 입사 레이저광은 대물렌즈(ㅧ100, NA = 0.7)를 통하여 샘플에 집광되었다. 라만 산란광은 동일한 대물렌즈에 모여서 분광계에 보내졌다. 각 스펙트럼을 획득하는 시간은 1분이었다. HRTEM 이미지들 및 EELS 스펙트럼을 측정하기 위하여, 가튼 이미징 필터(Gatan Imaging Filter)가 장착된 Cs-보정된 히타치 HD-2700 스캐닝 투과 전자 현미경이 이용되었다.
AlN powder is prepared by calcining (hydroxyl) (succinato) Al (III) ((hydroxo) (succinato) Al (III)) complexes at 1300 ° C. in a nitrogen gas atmosphere for 5 hours. The powder is contained in an alumina crucible and then placed in an alumina tube with an internal diameter of 36 mm and in a mixed gas of argon and 10 vol% carbon monoxide (hereinafter referred to as "10 vol% CO / Ar") flowing at 200 ml / min. Heated to 1400 ° C. at a rate of 5 ° C./min. This synthetic product was analyzed by powder XRD (PANalytical X'Pert PRO MPD X-ray diffractometer with Cu-Ka radiation operating at 40 kV and 30 mA). The carbon content in the synthesis product is determined by a CHN elemental analyzer (CHN elemental analyzer, Flash 1112, Thermo Fischer Scientific). Raman spectrum was measured by a micro Raman system. The incident laser light of the He-Ne laser (632.8 nm, 3 mW) was focused on the sample through the objective lens (# 100, NA = 0.7). Raman scattered light was collected in the same objective and sent to the spectrometer. The time to acquire each spectrum was 1 minute. To measure HRTEM images and EELS spectra, a Cs-corrected Hitachi HD-2700 scanning transmission electron microscope equipped with a Gartan Imaging Filter was used.
2. 그래핀 시트들로 싸인 알루미나 분말을 제조되는 DSSCs2. DSSCs made of alumina powder wrapped with graphene sheets
그래핀-TiO2 복합재 메소포러스 필름은, 그래핀 시트들에 싸인 알루미나 분말들 (1 wt%) 및 상용 TiO2 (P25) 나노분말을 함께 에탄올에 분산하고 페인트 쉐이킹(paint shaking)하여 제조되었다. 그래핀-TiO2 콜로이드는 바인더로서 에틸 셀룰로오스를 더해지고 그래핀-TiO2 페이스트의 용매로서 α-테르피네올이 더해진 상태에서 혼합기를 이용하여 분산되었고, 그 후 상기 혼합물은 증발기를 이용하여 농축하였다. 18㎛ 두께의 메소포러스 그래핀-TiO2층은, 기판 상에 전극층으로서 FTO(fluorine-doped tin oxide) TCO(transparent conducting oxide)을 형성하고, 이 위에 그래핀-TiO2 페이스트를 독터 블레이딩한 후, 450℃로 30분간 하소하여 제조되었다. 비교를 위하여, 그래핀 시트가 없는 18㎛ 두께의 메소포러스 TiO2 필름도 제조하였다. 광양극(photoanodes)은 염료 흡착을 위하여 밤새 N3 염료의 에탄올 용액에 담겨졌으며, 에탄올로 세정되고 50℃에서 건조되었다.Graphene-TiO 2 composite mesoporous film was prepared by dispersing alumina powders (1 wt%) and commercial TiO 2 (P25) nanopowders wrapped in graphene sheets together in ethanol and paint shaking. Graphene-TiO 2 colloid was dispersed using a mixer in which ethyl cellulose was added as a binder and α-terpineol as a solvent of the graphene-TiO 2 paste, and the mixture was then concentrated using an evaporator. . The 18 μm-thick mesoporous graphene-TiO 2 layer forms a fluorine-doped tin oxide (FTO) transparent conducting oxide (TCO) as an electrode layer on the substrate, and is interleaved with graphene-TiO 2 paste on the substrate. Then, it was prepared by calcining at 450 ℃ for 30 minutes. For comparison, an 18 μm thick mesoporous TiO 2 film without graphene sheets was also prepared. Photoanodes were soaked in ethanol solution of N3 dye overnight for dye adsorption, washed with ethanol and dried at 50 ° C.
그래핀 시트들로 싸인 알루미나 분말들을 가진 DSSCs 및 가지지 않는 DSSCs가, 백금 카운터 전극 (counter electrode) 및 전해액으로 제조되었다. 전해액은 아세토니트릴 용매에서 0.5 M 4-테르트-부틸피리딘(4-tert-butylpyridine), 0.6 M 3-헥실-1, 2-디메틸 이미다조리움 요드화물 (3-hexyl-1,2-dimethyl imidazolium iodide), 0.05 M 요오드, 0.05 M LiI로 구성되었다. 태양광 인텐서티 (100㎽/㎠, AM1.5) 하에서 상기 DSSCs의 광전기적 특성이 측정되었고, AIST-켈리브레이션된 Si 솔라셀 (PEC-L11, Peccell Technologies, Inc.)에 의하여 측정 결과가 검증되었다.
DSSCs with and without alumina powders wrapped with graphene sheets were made of platinum counter electrode and electrolyte. Electrolyte was prepared in 0.5 M 4- tert- butylpyridine, 0.6 M 3-hexyl-1, 2-dimethyl imidazolium iodide (3-hexyl-1,2-dimethyl imidazolium in acetonitrile solvent). iodide), 0.05 M iodine, 0.05 M LiI. The photoelectric properties of the DSSCs were measured under solar intensity (100 kW /
3. 실험 결과3. Experimental Results
검은 색의 생성 분말들은 AlN 분말들(도 1(a) 참조)을 10 vol% CO/Ar의 흐름 하에서 1400℃에서 하소하여 제조되었다. 5시간 반응 후 얻어진 샘플(이하, "샘플A"라 한다)의 XRD 패턴(도 1(b) 참조)은, AlN(JCPDS Card No. 25-1133)에서의 회절 피크와 함께 d-Al2O3(JCPDS Card No.46-1131)의 약한 회절 피크를 보여주었다. 20시간 반응 후 얻어진 샘플(이하, "샘플B"라 한다)의 XRD 패턴(도 1(c) 참조)은, AlN, d-Al2O3 및 a-Al2O3(JCPDS Card No.46-1212)의 회절 피크를 보여주었다. 샘플 A 및 샘플 B에서의 카본 함유량은 각각 2.7 및 5.2 wt%였으며, 이는 2개의 샘플들의 검은 색이 탄소에 기인함을 보여주었다. 합성된 분말에서 Al2O3과 탄소가 검출된 것으로 보아 1400℃에서 반응식1의 역반응이 일어났음을 알 수 있다. Black product powders were prepared by calcining AlN powders (see FIG. 1 (a)) at 1400 ° C. under a flow of 10 vol% CO / Ar. The XRD pattern (see Fig. 1 (b)) of a sample obtained after 5 hours reaction (hereinafter referred to as “sample A”) is d-Al 2 O with diffraction peaks in AlN (JCPDS Card No. 25-1133). A weak diffraction peak of 3 (JCPDS Card No. 46-1131) was shown. The XRD pattern (see Fig. 1 (c)) of the sample obtained after 20 hours reaction (hereinafter referred to as "sample B") is AlN, d-Al 2 O 3 and The diffraction peak of a-Al 2 O 3 (JCPDS Card No.46-1212) was shown. The carbon content in Sample A and Sample B was 2.7 and 5.2 wt%, respectively, showing that the black color of the two samples was due to carbon. Al 2 O 3 and carbon in the synthesized powder From the detection, it can be seen that the reverse reaction of
도 1(b) 및 (c)를 참조하면, 탄소 물질에는 회절 피크가 관측되지 않았다. 상기 탄소 물질의 정체를 확인하기 위하여, 상기 생성물 분말의 라만 스펙트럼(Raman spectrum)을 측정하였다. 1 (b) and (c), no diffraction peaks were observed in the carbon material. In order to confirm the identity of the carbon material, the Raman spectrum of the product powder was measured.
도 2를 참조하면, 샘플 A 및 B의 라만 스펙트럼은 그래핀 시트들의 3가지 특징적 밴드들을 잘 보여준다. 이는 D (샘플 A 및 B에서 각각 1314 and 1317 cm-1 임), G (샘플 A 및 B에서 각각1588cm-1 임), 및 2D(샘플 A 및 B에서 각각 2614cm-1 및 2624cm-1 임)이었다. 도 2(a)에서 2870cm-1의 약하고 넓은 밴드는 D+G의 결합 밴드이었다. 도 1(b) 및 (c)에서 보이는 그래핀 시트들에 대한 회절 피크가 보이지 않는다는 것은, 적은 수의 그래핀층들 및/또는 그래핀 시트들의 낮은 결정도에 기인하였다. Referring to FIG. 2, the Raman spectra of Samples A and B show three characteristic bands of graphene sheets. This D (samples A and, respectively 1314 and 1317 cm -1 being in B), G (samples A and B respectively at 1588cm -1 Im), and 2D (sample A, and each of 2614cm -1 and 2624cm -1 game, B) It was. In FIG. 2 (a), the weak and broad band of 2870 cm −1 was the binding band of D + G. The absence of diffraction peaks for the graphene sheets shown in FIGS. 1 (b) and (c) was due to the low crystallinity of the small number of graphene layers and / or graphene sheets.
샘플 A의 라만 스펙트럼 (도 2(a))의 밴드 패턴은 10 vol% CO/Ar 분위기하에서 Al2S3를 10시간 동안 1100℃에서 하소시켜서 얻은 그래핀 시트의 것과 유사하였다. The band pattern of the Raman spectrum of Sample A (FIG. 2 (a)) was similar to that of the graphene sheets obtained by calcining Al 2 S 3 at 1100 ° C. for 10 hours under 10 vol% CO / Ar atmosphere.
샘플 B에서의 그래핀 시트들은 80 ㎸에서 작동하는 고 분해능 투과 전자 현미경(HRTEM)에 의하여 특징이 파악되었다. 도 3(a)를 참조하면, 평행하는 어두운 프린지들(fringes)이 샘플 B 분말들의 가장자리에서 발견되었다. 인접하는 프린지들 사이에서의 간격은 0.34㎚이었는데, 이는 흑연의 (002)면들 사이에서의 간격과 일치했다. 카본 K-에지(carbon K-edge)에서의 EELS 스펙트럼을 상기 프린지들이 그래핀 시트들에서 기인하는 것임을 확실하게 하기 위하여 측정하였다. 도 3(b)를 참조하면, 상기 프린지들(도 3(a)에서 ⓐ위치)의 EELS 스펙트럼은 카본 K-에지 영역에서 흑연의 EELS 스펙트럼의 특징을 보여주었다. 287, 294 eV에서의 피크들은 각각 1s에서 π* 및 σ*으로의 전이에 기인한다. 상부면(도 3(a)에서 ⓑ 위치)의 EELS 스펙트럼 또한 흑연 EELS 스펙트럼의 특징을 보여주었다. 도 3(b)의 EELS 스펙트럼은 수 층의 그래핀 시트들이 알루미나 분말들을 싸고 있는 상태를 보여주었다. Graphene sheets in Sample B were characterized by high resolution transmission electron microscopy (HRTEM) operating at 80 Hz. Referring to Figure 3 (a), parallel dark fringes were found at the edges of Sample B powders. The spacing between adjacent fringes was 0.34 nm, which coincided with the spacing between (002) planes of graphite. EELS spectra at carbon K-edges were measured to ensure that the fringes are due to graphene sheets. Referring to Figure 3 (b), the EELS spectrum of the fringes (ⓐ position in Figure 3 (a)) showed the characteristics of the EELS spectrum of graphite in the carbon K-edge region. Peaks at 287 and 294 eV are due to the transition to π * and σ * at 1s, respectively. The EELS spectrum of the top surface (the ⓑ position in Fig. 3 (a)) also showed the characteristics of the graphite EELS spectrum. The EELS spectrum of FIG. 3 (b) showed that a few layers of graphene sheets wrapped the alumina powders.
도 4에 상기 그래핀 시트들에 싸인 알루미나 분말들을 가지는 DSSCs 및 이를 가지지 않는 DSSCs에서의 광전류 밀도-전압 곡선이 제시되어 있다. 그래핀-TiO2 복합제 전극을 가지는 DSSC는 전체 에너지 변환 효율이 4.6%에서 5.1%로 11% 증가하였다. 이는 주로 단락 전류(short circuit current)의 증가에 기인한다. 상기 그래핀 시트들에 싸인 알루미나 분말들이 TiO2 나노분말들과 혼합되어 효과적인 전자 이동 매체로서 작용하는데, 이에 의하여 TiO2로부터 FTO로 전자 이동이 증가하도록 함과 아울러 상기 재결합률을 낮추게 한다. 이러한 작용은, 그래핀의 일 함수(work function)가 TiO2의 전도도 밴드보다 낮고, 그래핀의 전기 전도도가 높기 때문이다.4 shows photocurrent density-voltage curves in DSSCs with and without alumina powders wrapped in the graphene sheets. DSSC with graphene-TiO 2 composite electrode increased 11% from 4.6% to 5.1% overall energy conversion efficiency. This is mainly due to the increase in short circuit current. The alumina powders wrapped in the graphene sheets are mixed with TiO 2 nanopowders to act as an effective electron transfer medium, thereby increasing the electron transfer from TiO 2 to FTO and lowering the recombination rate. This action is because the work function of graphene is lower than the conductivity band of TiO 2 , and the electrical conductivity of graphene is high.
이렇게 그래핀 시트들에 싸인 알루미나 분말들은 DSSCs, 광촉매, 광전기화학 물 분해 셀(photoelectrochemical water-splitting cells)에 이용될 수 있을 것이다.
These alumina powders wrapped in graphene sheets could be used for DSSCs, photocatalysts and photoelectrochemical water-splitting cells.
본 발명은 도면에 도시된 실시예를 참고로 설명되었으나 이는 예시적인 것에 불과하며 본 기술 분야의 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 다른 실시예가 가능한 점을 이해할 것이다. 따라서, 본 발명의 진정한 기술적 보호범위는 첨부된 특허청구범위의 기술적 사상에 의하여 정해져야 할 것이다.Although the present invention has been described with reference to the embodiments shown in the drawings, these are merely exemplary and those skilled in the art will understand that various modifications and equivalent other embodiments are possible. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.
Claims (10)
(b) 상기 AlN 분말들을 부분 또는 전체로서 일산화탄소 가스와 아르곤 가스를 포함하는 반응가스 분위기에서 하소(calcining)하되, 상기 반응 가스가 설정 속도로 흐르고 있는 상태에서, 상기 AlN 분말들을 점차 가열하여 온도를 상승시키는 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계를 포함하는 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 방법.(a) preparing AlN powders; And
(b) calcining the AlN powders in a reaction gas atmosphere containing carbon monoxide gas and argon gas as part or all, and while the reaction gas is flowing at a set rate, the AlN powders are gradually heated to increase the temperature. A method of making alumina powders wrapped with graphene sheets comprising the step of making alumina powders wrapped with elevating graphene sheets.
(b) 상기 AlN 분말들과 일산화탄소 가스 사이의 열탄소환원질화 반응(carbothermal reduction and nitridation)의 역반응을 통하여, 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 방법.(a) preparing AlN powders; And
(b) A method for producing alumina powders wrapped with graphene sheets through a reverse reaction of carbonaceous reduction and nitridation between the AlN powders and carbon monoxide gas.
상기 AlN 분말들과 일산화탄소 가스 사이의 열탄소환원질화 반응(carbothermal reduction and nitridation)의 역반응을 통하여 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계; 및
상기 알루미나 분말들과 TiO2 나노분말들의 혼합 분말을 이용하여 그래핀-TiO2 페이스트를 제조하는 단계를 포함하는 그래핀-TiO2 페이스트 제조 방법.Preparing AlN powders;
Preparing alumina powders wrapped with graphene sheets through a reverse reaction of carbonaceous gas reduction and nitridation between the AlN powders and carbon monoxide gas; And
Graphene-TiO2 paste manufacturing method comprising the step of preparing a graphene-TiO2 paste using the mixed powder of alumina powders and TiO2 nanopowders.
상기 AlN 분말들과 일산화탄소 가스 사이의 열탄소환원질화 반응(carbothermal reduction and nitridation)의 역반응을 통하여 그래핀 시트들로 싸인 알루미나 분말들을 제조하는 단계;
상기 알루미나 분말들과 TiO2 나노분말들의 혼합 분말을 이용하여 그래핀-TiO2 페이스트를 제조하는 단계;
기판 상에 전극층을 형성하는 단계; 및
상기 전극층 상에 상기 그래핀-TiO2 페이스트를 도포하여 TiO2층을 형성하는 단계를 포함하는 염료 감응형 태양전지의 제조방법.Preparing AlN powders;
Preparing alumina powders wrapped with graphene sheets through a reverse reaction of carbonaceous gas reduction and nitridation between the AlN powders and carbon monoxide gas;
Preparing a graphene-TiO 2 paste using a mixed powder of the alumina powders and the TiO 2 nanopowders;
Forming an electrode layer on a substrate; And
A method of manufacturing a dye-sensitized solar cell comprising applying the graphene-TiO 2 paste on the electrode layer to form a TiO 2 layer.
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